Calcination process to produce enhanced odh catalyst

ABSTRACT

Mixed metal oxide catalysts having an amorphous content of not less than 40 wt. % are prepared by calcining the catalyst precursor fully or partially enclosed by a porous material having a melting temperature greater than 600° C. in an inert container including heating the catalyst precursor at a rate from 0.5 to 10° C. per minute from room temperature to a temperature from 370° C. to 540° C. under a stream of pre heated gas chosen from steam and inert gas and mixtures thereof at a pressure of greater than or equal to 1 psig having a temperature from 300° C. to 540° C. and holding the catalyst precursor at that temperature for at least 2 hours and cooling the catalyst precursor to room temperature.

This application claims the benefit of the earlier filing date of Canadian application serial number CA 2 999 092 filed on Mar. 26, 2018, the contents of which are incorporated herein by reference in their entirety.

The present disclosure relates to a controlled calcination process to produce an enhanced catalyst for the oxidative dehydrogenation for paraffins to olefins, particularly lower paraffins such as C₂₋₄ paraffins to the corresponding olefins. Mixed metal oxide catalysts for the dehydrogenation of paraffins have been known since the mid to late 1960′s. The catalyst activity and selectivity depend more on the content of amorphous phase (sometimes referred to as the M2 phase) versus crystalline phase(s) (sometimes referred to as M1 phase) of the catalyst.

Over about the past 10 years there has been increasing interest in the mixed metal oxide catalyst including Mo, V, Nb and one or more of Te and Sb optionally together with one or more of Pd, Sb Ba, Al, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, and Ca.

In some embodiments the present disclosure provides a method to calcine a mixed metal oxide oxidative dehydrogenation catalyst. In some embodiments of the present disclosure amorphous content remains high, for example greater than 40 wt. %, or for example above 50 wt. %.

In some embodiments, the present disclosure provides a method to calcine a catalyst precursor of the formula Mo₁V_(0.1-1)Nb_(0.1-1)Te_(0.01-0.2)X₀₋₂O_(d) where X is chosen from Pd, Sb Ba, Al, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, Ca and oxides thereof and mixtures thereof, and d is a number to satisfy the valence of the catalyst while maintaining an amorphous content of not less than 40 wt. %, the method including:

Calcining the catalyst precursor in an inert container with flow passage there through, including heating the catalyst precursor at a rate from 0.5 to 10° C. per minute from room temperature to a holding temperature from 370° C. to 540° C. under a stream of pre heated gas chosen from steam and inert gas and mixtures thereof at a rate of flow comparable to a flow rate of not less 150 sccm through a 2.54 cm diameter tube, with a length of 152 cm at a pressure of greater than or equal to 1 psig having a temperature of at least 100° C. in some embodiments from 300° C. to 540° C. and holding the catalyst precursor at the holding temperature for at least 2 hours and cooling the catalyst precursor to room temperature said catalyst precursor being fully or partially enclosed by a porous material having a melting temperature greater than 600° C.

In a further embodiment, the inert container is made from high temperature glass (e.g. Pyrex), quartz, ceramics (Beryllium Oxide), alumina), or steel.

In a further embodiment, the inert container has a heat conductivity greater than 0.34W·m⁻¹·K.

In a further embodiment, the flow rate of preheated gas is greater than 150 sccm.

In a further embodiment, the pressure of inert gas greater than 1 psig.

In a further embodiment the heat up rate is 0.9 to 2.0 C per min.

In a further embodiment, the catalyst precursor is held at the holding temperature from 2 to 24 hours.

In a further embodiment, the holding temperature is from 400° C. to 525° C.

In a further embodiment, the inert gas includes nitrogen.

In a further embodiment, the porous material is chosen from glass and mineral fiber.

In a further embodiment, optionally charcoal or activated carbon is on the outer surface of the porous material in an amount up to 0.5 g per 1 g of catalyst precursor.

In a further embodiment X is one or more metals and oxides thereof chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof.

In a further embodiment the molar ratio of said one or more metals and oxides chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof to Mo is from 1:0.001 to 0.3, for example, from 1:0.05 to 0.15.

In a further embodiment X is chosen from one or more metals and oxides thereof are chosen from Pd, Sb, Ba, Al, Cu and mixtures thereof.

In a further embodiment in the catalyst, precursor X is absent.

In a further embodiment, the catalyst precursor has the formula:

Mo_(1.0)V_(0.10-049)Te_(0.06-0.17)Nb0.13-0.19O_(d).

In a further embodiment, the calcined catalyst has the formula:

Mo₁V_(0.40-0.45)Te_(0.10-0.16)Nb_(0.13-0.16)O_(d).

In a further embodiment, the calcined catalyst has the formula

MoV_(0.40-0.45)Te_(0.10-0.16)Nb_(0.13-0.16)O_(d).

having an amorphous content of not less than 40 wt. %.

In a further embodiment, the calcined catalyst has a crystallite size calculated according to the Scherrer equation of 45 to 55 nm.

In a further embodiment, the calcined catalyst has a crystallite size calculated according to the Scherrer equation of 50 to 52 nm.

In a further embodiment, the calcined catalyst is bound, agglomerated, filled, promoted, impregnated, or supported with from 5 -90, wt. % of a material other than active phase.

A further embodiment provides a method for the oxidative dehydrogenation of a mixed feed including one or more C₂₋₄ paraffins and oxygen in a volume ratio from 70:30 to 95:5 and optionally one or more C₃₋₆ alkanes or alkenes and oxygenated species including CO and CO₂ at a temperature from 320° C. up to 385° C., a gas hourly space velocity of not less than 100 hr⁻¹, and a pressure from 0.8 to 7 atmospheres including passing said mixture over the above catalyst (s).

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram of the location of the samples of catalyst precursor in the quartz tube reactor showing the heating zones and the flow of nitrogen.

FIG. 2 is an XRD of an uncalcined (low calcined) catalyst of boat 4 with an underlying base line for the calcined sample.

FIG. 3 is a plot of the conversions and selectivity of the catalyst for ethane to ethylene at various temperatures over a long term run of about 650 hours.

FIG. 4 is plot of the pore size distribution of the catalysts of the present disclosure.

NUMBERS RANGES

Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, etc. used in the specification and claims are to be understood as modified in all instances by the term “about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the properties that the present disclosure desires to obtain. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.

All compositional ranges expressed herein are limited in total to and do not exceed 100 percent (volume percent or weight percent) in practice. Where multiple components can be present in a composition, the sum of the maximum amounts of each component can exceed 100 percent, with the understanding that, and as those skilled in the art readily understand, that the amounts of the components actually used will conform to the maximum of 100 percent.

In the specification, the phrase the temperature at which there is 25% conversion of ethane to ethylene is determined by plotting a graph of conversion to ethylene against temperature typically with data points below and above 25% conversion or the data is fit to an equation and the temperature at which there is a 25% conversion of ethane to ethylene is determined. In some instances, in the examples the data had to be extrapolated to determine the temperature at which 25% conversion occurred.

In the specification, the phrase selectivity at 25% conversion is determined by plotting the selectivity as function of temperature or fit to an equation. Then having calculated the temperature at which 25% conversion occurs one can determine either from the graph or from the equation the selectivity at that temperature.

The ratio of amorphous component to crystalline component may be determined by obtaining an XRD for the calcined catalyst. Within 24 hours of obtaining the sample XRD a standard (100% crystalline material such as Corundum) is run on the XRD instrument to determine the K factor for the instrument. Then knowing the K factor the percentage of crystalline phase per unit mass of sample and the difference is the weight of the amorphous content per unit mass of sample is determined. Such as disclosed in O. Connor and Raven (1988), Powder Diffraction, 3(1), 2-6; http://www.icdd.com/ppxrd/12/presentations/P30-Arnt-Kern-ppxrd-12.pdf.

A typical procedure is as follows:

-   -   1. The sample is finely ground to reduce particle size to less         than 250 microns and obtain a uniform mixture.     -   2. The ground sample is loaded onto an XRD sample holder         preferably having an EDS stub for XRD and EDS analysis.     -   3. Acquire the XRD spectrum and where applicable perform EDS         analysis using a scanning electron microscope (SEM).     -   4. Combine Highscore Plus, EDS and Rietveld Refinement to         perform qualitative and quantitative analysis.     -   5. Amorphous analysis—Run standard using exactly same holder and         same program as with the sample. Standard must be run with 24         hrs after the sample was run.     -   6. Using external standard method to determine the amorphous         content.     -   7. With an external standard method an instrument intensity         constant often called K-factor (sometimes called G-factor as         well) is determined. The instrument and software already have a         program set up for this method.     -   8. Generate report.

In this specification non-antagonistic binder means a binder other than Nb₂O₅ which when incorporated into the agglomerated catalyst has less than a 5% antagonistic effect on the agglomerated catalysts. Some non-antagonistic binders include oxides of aluminum, titanium and zirconium. Silica oxides have an antagonistic effect on the agglomerated catalysts and the catalyst active sites.

The Catalyst Precursor

The catalyst precursor may be prepared using a hydrothermal process including following steps:

i) forming an aqueous solution of ammonium heptamolybdate (tetrahydrate) and telluric acid in a molar ratio of Mo:Te of 1:0.14 to 0.20, in some instances from 1:0.17, at a temperature from 30° C. to 85° C. and adjusting the pH of the solution to 6.5 to 8.5, for example, from 7.0 to 8.0, for example, from 7.3 to 7.7, for example, with a nitrogen-containing base to form soluble salts of the metals;

ii) stirring the pH adjusted solution for a time of not less than 15 minutes, in some instances from not less than 2 hours, in some instances not more than 4 hours;

iii) adjusting the pH of the resulting solution to from 4.5 to 5.5, for example, from 4.8 to 5.2, for example from 5.0 to 5.2 with an acid, for example, sulfuric acid (0.01-18 M, typically 2-18 M) and stir the resulting solution at a temperature of 80° C. until it is homogeneous in some instances with a stirring time up to 30 minutes; In some circumstances, to maintain 80° C. temperature, a cooling device needs to be used to maintain temperature at 80° C.

iv) preparing an aqueous solution of vanadyl sulphate at a temperature from room temperature to 80° C. (for example, 50° C. to 70° C., for example, 55° C. to 65° C.);

v) mixing the solutions from steps i) and iv) together to provide a molar ratio of V:Mo from 1.00-1.67 to 1 in some cases from 1.45-1.55 to 1.00;

vi) preparing a solution of H₂C₂O₄ and Nb₂O₅xH₂O in a molar ratio from 5.0 to 6:0, in some instances 5.0-5.3:1;

vii) slowly (i.e. dropwise) adding the solution from step vi) to the solution of step vi) to provide molar ratio of Nb:Mo from 5.56-7.14:1 in some instances from 6.20-6.40 to form a slurry (typically the addition is at temperatures between 20° C. and 80° C.; for example, 20° C. to 30° C.); and

vii) heating the resulting slurry in an autoclave under an inert gas, air, carbon dioxide, carbon monoxide and mixtures there-of at a pressure of not less than 1 psig and at a temperature from 140° C. to 190° C. for not less than 6 hours, or for example, not less than 6 hours and not more than 36.

The temperature for the hydrothermal treatment may range from 140° C. to 180° C., in some embodiments from145° C. to 175° C.

The pressure in the autoclave may range from equal or above the saturated water vapor pressure at the corresponding reaction temperature in some embodiments from 30 to 200 psig (206 kPag to 1375 kPag), in some embodiments from 55 psig (380 kPag) to 170 psig (1170 kPag) above atmospheric pressure. The gaseous product species can be vented from the autoclave (reactor).

Optionally there is a condenser upstream of the autoclave outlet which may be operated at a temperature above 0° C. and below reaction temperature.

In some embodiments, the pressure inside the autoclave may be maintained above atmospheric using a liquid filled column or bubbler or a pressure regulator valve.

In some embodiments, the hydrothermal treatment may be from 6 to 15 hours.

In some embodiments, the autoclave (reactor) is allowed to cool to room temperature, typically overnight. The reactor contents are filtered using a Buchner filter and washed with (distilled) water or an aqueous oxalic acid solution and dried in an oven for not less than 6 hours at a temperature from 70° C. to 120° C.

In some embodiments, the precatalyst is separated from the aqueous phase, for example, by filtration or evaporation, and washed with (distilled or deionized) water and dried in an oven for not less than 6 hours at a temperature from 70° C. to 120° C. The precatalyst may be dried in an atmosphere including one or more inert gases. In some instances, optionally, the dried precatalyst may be ground using mechanical means (e.g. a ball or roller mill) or the dried precatalyst could be subject to cryogenic grinding. The dried and ground precatalyst may in some instances be subject to sieving through a small particle size sieve to obtain a fraction having a particle size less than 250 microns, for example, less than 125 microns.

In some embodiments, the product from the hydrothermal treatment is treated with from 0.3-2.5 mL of a 30 wt. % solution of aqueous H₂O₂ per gram of catalyst precursor.

In some embodiments, the catalyst precursor (i.e. prior to calcining) has the formula:

Mo₁V_(0.1-1)Nb_(0.1-1)Te_(0.01-0.2)X₀₋₂O_(d)

where X is chosen from Pd, Sb Ba, Al, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, Ca and oxides and mixtures thereof, and d is a number to satisfy the valence of the catalyst precursor. In some embodiments X is chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof. In some embodiments, X is chosen from Pd, Sb, Ba, Al, Cu and mixtures thereof. In the formula for the precursor the molar ratio of said one or more metals and oxides and mixtures thereof to Mo is up to 2, typically if X is present from 0.001-0.3, for example, from 0.05-0.15.

In some embodiments, X is absent from the catalyst precursor and it has the formula:

Mo_(1.0)V_(0.10-0.49)Te_(0.06-0.17)Nb_(0.13-0.19)O_(d) where d is a number to satisfy the valence of the catalyst precursor.

In some embodiments, the reactor is allowed to cool to room temperature, typically overnight. The reactor contents were filtered using a Buchner filter and washed with (distilled) water or an aqueous oxalic acid solution and dried in an oven for not less than 6 hours at a temperature from 70° C. to 120° C. The dried precatalyst can be ground, typically to a size less than 250 μm and calcined in an inert atmosphere such as nitrogen for a time from 1 to 20 hours.

The catalyst precursor can be calcined in an inert container with a flow passage there through, including heating the catalyst precursor at a rate from 0.5 to 10° C. per minute in some embodiments from 0.9 to 2 C per minute from room temperature to a temperature from 300° C. to 540° C., in some cases from 400° C. to 525° C., under a dynamic stream of optionally preheated inert gas such as nitrogen, helium, etc. and mixtures thereof at a flow rate of nitrogen comparable to (based upon) a flow of nitrogen through a 1 inch internal diameter tube having a length of 152 cm (59.8 inches) at a flow rate from 200-500 sccm per 30-250 gram of catalyst precursor.

The inert container may have a heat conductivity greater than 0.34 Wm⁻¹·K⁻¹, in some embodiments from 1.2 W·m⁻¹·K⁻¹ to 50 W·m⁻¹·K⁻¹. The container may be made from high temperature glass (e.g. Pyrex), quartz, ceramics (e.g. beryllium oxide), alumina), steel, for example, a low carbon steel or a grade of stainless steel.

In some embodiments, the inert gas (e.g., nitrogen) in the calcination chamber is not static. In some embodiments, it is dynamic and flows over the precatalyst. Flow rates are a function of many variables such as the shape of the chamber, the size of the opening and exit ports of the chamber, the pressure drop across the inlets and outlets. One skilled in the art or having access to computational fluid dynamic programs can calculate flow rates. However, some starting point for the calculation is required. A starting point is the flow rate for a tubular drying chamber (tube) having a one inch (2.54 cm) internal diameter and a length of 152 cm (59.8 inches) is from 200-500 sccm per 30-250 gram of catalyst precursor. In some instances, the flow rate may be equivalent to a flow rate through a 1 inch diameter tubular drying chamber having a length of 152 cm from 250 to 450 sccm per 30-250 gram of catalyst precursor. However, the flow rate needs to be increased as the chamber volume increases.

The pressure in the interior of the flow chamber should be at least 1 psig (6.9 kPag) in some instances from 1 to 5 Psi, in some cases, higher than 5psi.

The temperature of the gas flowing through the chamber is from 300° C. to 540° C. (in some cases from 400° C. to 525° C.). The temperature of the inert gas flowing over the catalyst is influenced by the temperature of the calcination and the flow rate.

In some embodiments, the catalyst precursor is held at the calcining temperature for at least 2 hours, or for example, from 2-24 hours and cooled to room temperature.

During the calcining process the catalyst precursor may be at least partially enclosed in a breathable or permeable covering. In some embodiments it is preferred that the covering substantially encloses the catalyst precursor (e.g. at least 50% or for example not less than 75% of the external surface of the catalyst precursor is covered by the breathable or permeable covering). The covering can have a permeability to gas from 5 cubic feet per minute (8.5 cubic meter/h) to 100 cubic feet per minute (170 cubic meter/hour) in some cases from 10 cubic feet per minute to 60 cubic feet per minute according to the measurement method specified by ASTM E2945-14. The permeable covering should have a melting point greater than 600° C. Provided the covering is breathable or permeable it may be a woven or nonwoven material. For example, it could be a plastic or metallic (or a metalized plastic substrate) substrate having a melting point above 600° C. Permeability could be provided by any mechanical means to permit the passage of gas through the covering such as needle type punching process. The permeable covering could be a non-woven chosen from polymers having a melting point above 600° C. and glass and mineral fiber, for example, glass and mineral fiber (e.g. fiber glass batting). If the covering is a woven fabric, the permeability would be controlled by the tightness of the weaving of the fabric. For example, the fabric could have up to 960 of pores per cm² for multifilament woven fabric.

In some embodiments activated carbon (greater than 90%, of for example greater than 95% purity) may be placed on top of the permeable covering to scavenge oxygen and materials released from the catalyst. The carbon may be used in amounts up to 0.5 g, typically 0.1 to 0.3 g per 1 g of catalyst precursor being calcined.

The catalysts prepared in accordance with the present disclosure have an x-ray diffraction pattern (XRD having) typically associated with a polycrystalline (broad reflection peaks) structure vs. predominantly crystalline material (narrow reflection peaks), which is characteristic of the classical catalyst. It is the common belief in the literature that the active phase is the crystalline MoVNbTeOx phase referred to as M1 (narrow reflection peaks) as opposed to the broad smoother reflection peaks of the present catalyst. The XRD for a typical ODH catalyst has the intense diffraction angles) at 2 Φ (Cu source) at 22° having a half height peak width from 19° to 21° and broad secondary peak at 28° having a half width from 25° to 33°. Generally, the typical ODH catalyst has a crystallite size (τ) of about 90 nm. Whereas the Inventive Example has a crystallite size of from 45 nm to 55 nm, typically 48 to 52 nm, in some cases 50±1 nm. Crystallite size is calculated using the Scherrer equation, where K (dimensionless shape factor) is assumed to be 1, λ is the X-ray wavelength from Copper source and is 1.5406 Å, θ is the Bragg angle of 22.29°, and β is the line broadening at half the maximum intensity (FWHM) as determined for the XRD data.

The catalysts in accordance with the present disclosure demonstrate a higher amorphous component not less than 40 wt. %, in some embodiments not less than 50 wt. %, for example greater than 60 wt. % or for example greater than 70 wt. %.

The catalysts of the present disclosure have a smaller pore size than those of the base line. The catalysts made in accordance with the present process have a majority of pores having a size less than 10 nm. Catalysts prepared without the calcination of the present disclosure tend to have relatively flat pore size distribution.

In a further embodiment, from 10 wt. % to 95 wt. %, for example from 25 wt % to 80 wt. %, or for example from 30 wt% to 45 wt. %, of the catalyst is bound, agglomerated, filled, promoted, impregnated, or supported with from 5 wt. % to 90 wt. %, for example from 20 wt. % to 75 wt. %, or for example from 55 wt. % to 70 wt. % of a material (for example, a binder) other than active phase chosen from slurries of TiO₂, ZrO₂ Al₂O₃, AlO(OH), Nb₂O₅ and mixtures thereof, where the slurries can be acidic, basic or neutral binder slurries, and provided that ZrO₂ is not used in combination with an aluminum containing binder.

In a further embodiment, there is provided a method for the oxidative dehydrogenation of a mixed feed including a C₂₋₄ paraffin (e.g., ethane) and oxygen in a volume ratio from 70:30 to 95:5 and optionally one or more C₃₋₆ alkanes or alkenes and oxygenated species including CO and CO₂ at a temperature greater than 320° C. up to than 385° C., a gas hourly space velocity of not less than 100 hr⁻¹, and a pressure from 0.8 to 7 atmospheres including passing said mixture over the above catalyst.

In a further embodiment, the ODH process has a selectivity to ethylene of not less than 85%.

In a further embodiment, the gas hourly space velocity of the ODH process is not less than 500 hr⁻¹ for example, not less than 1500 hr⁻¹ in some embodiments 3000 hr⁻¹.

In a further embodiment, the temperature of the ODH process is less than 375° C., for example, less than 360° C.

The catalysts prepared using the calcining procedure of the present disclosure are more robust than comparable catalysts prepared using a conventional calcination method (higher temperatures and no non-woven covering no carbon) and maintains it activity albeit as a slightly lower selectivity than a catalyst calcined in a conventional process. The catalysts may also be regenerated in situ in the oxidative dehydrogenation reactor by passing oxygen, air optionally in combination with one or more inert gasses over the catalyst.

In one embodiment, the present disclosure provides a method to calcine a catalyst precursor of the formula Mo₁V_(0.1-1)Nb_(0.1-1)Te_(0.01-0.2)X₀₋₂O_(d) where X is chosen from Pd, Sb Ba, Al, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, Ca and oxides and mixtures thereof, and d is a number to satisfy the valence of the catalyst while maintaining an amorphous content of not less than 40 wt. % including calcining the catalyst precursor in an inert container with flow passage there through, including heating the catalyst precursor at a rate from 0.5 to 10° C. per minute from room temperature to a temperature from 370° C. to 540° C. under a stream of pre heated gas chosen from steam and inert gas and mixtures thereof at a rate of flow comparable to a flow rate of not less 150 sccm through a 2.54 cm diameter tube, with a length of 152 cm at a pressure of greater than or equal to 1 psig having a temperature from 300° C. to 540° C. and holding the catalyst precursor at that temperature for at least 2 hours and cooling the catalyst precursor to room temperature the catalyst precursor being fully or partially enclosed by a porous material having a melting temperature greater than 600° C.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the inert container is made from high temperature glass, quartz, ceramics, or steel.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the inert container has a heat conductivity greater than 0.34W m⁻¹˜K.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the flow rate of inert gas and mixtures thereof is greater than 150 sccm.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the pressure of inert gas greater than 1 psig.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the heat up rate is 0.9 to 2.0 C per min

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the catalyst precursor is held at a temperature from 2-24 hours.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the catalyst is held at a temperature from 400° C. to 525° C.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the stream of inert gas and mixtures thereof includes nitrogen.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the porous material is chosen from glass and mineral fiber.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein optionally charcoal or activated carbon is on the outer surface of the porous material in an amount up to 0.5 g per 1 g of catalyst precursor is present on the upper surface of the material.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein X is one or more metals and oxides thereof are chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the molar ratio of said one or more metals and oxides chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof to Mo is from 1:0.001-0.3, for example, from 1:0.05-0.15.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein the X is chosen from one or more metals and oxides thereof are chosen from Pd, Sb, Ba, Al, Cu and mixtures thereof.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method wherein in the catalyst precursor X is absent.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a catalyst precursor having the formula:

Mo_(1.0)V_(0.10-049)Te_(0.06-0.17)Nb_(0.13-0.19)O_(d).

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a calcined catalyst of the formula:

Mo₁iV_(0.40-0.45)Te_(0.10-0.16)Nb_(0.13-0.16)O_(d).

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a calcined catalyst of the formula

Mo₁V_(0.40-0.45)Te_(0.10-0.16)Nb_(0.13-0.16)O_(d)

having an amorphous content of not less than 40 wt. %.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a calcined catalyst having a crystallite size calculated according to the Scherrer equation of 45 to 55 nm.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a calcined catalyst having a crystallite size calculated according to the Scherrer equation of 50 to 52 nm.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a calcined catalyst bound, agglomerated, filled, promoted, impregnated, supported with from 5-90 wt. % of a material other than active phase.

In a further embodiment, the present disclosure provides in combination with one or more other embodiments a method for the oxidative dehydrogenation of a mixed feed including one or more C₂₋₄ paraffins and oxygen in a volume ratio from 70:30 to 95:5 and optionally one or more C₃₋₆ alkanes or alkenes and oxygenated species including CO and CO₂ at a temperature from 320° C. up to 385° C., a gas hourly space velocity of not less than 100 hr⁻¹, and a pressure from 0.8 to 7 atmospheres including passing said mixture over a catalyst as above.

EXAMPLES

An oxidative dehydrogenation catalyst was prepared using the following hydrothermal process.

Hydrothermal Synthesis:

259.4 g of (NH₄)₆Mo₆TeO₂.7H₂O (s) was dissolved in 600 mL of de-ionized water in a 2 L three neck round bottom flask (RBF), with a stir rate of 750 rpm with the addition of a warm water bath

189.11 g of VOSO₄.3.41H₂O (s) was dissolved in 300 mL of de-ionized water, with the addition of a warm water bath

194.35 g of H₃[NbO(C₂O₄)₃]_((soln.)) was weighed into a 250 mL beaker and held for later use

VOSO₄.3.41H₂O_((aq)) solution was added to the (NH₄)₆Mo₆TeO₂.7H₂O_((aq)) solution in the 1 L RBF

Solution turned black

Solution was left to stir for 30 minutes, after which the solution turned a purple color

All manipulations were performed in air

194.35 g of H₃[NbO(C₂O₄)₃]_((soln.)) was added to a 250 mL addition funnel, affixed to the 3 neck RBF

Solution was added dropwise to the agitating purple slurry (60 minutes for addition time)

Solution remained as a dark purple slurry

Solution was transferred to a 1 L glass liner inside a 1 L PARR autoclave

Autoclave set up was sealed and purged 10 times with repeating N_(2 (g)) evacuation sequences

Autoclave was connected to the condenser set up

Reaction was left to stir overnight in the autoclave set up at room temperature

The following day the PARR autoclave was hated to 175° C., the autoclave reached a temperature of 172° C. after 48 hours

Reaction mixture was left to heat in the autoclave set up overnight at 175° C. with the condenser set up

The following day the temperature was set back to room temperature

Reaction set up was not cooled by the end of the day and was left to cool over the weekend

After the reaction was cooled it was depressurized and filtered through 4× Whatmann 4 filter paper media

The filter cake was rinsed with approximately 0.5 L of deionized water until the filtrate ran clear

Filtration time was approximately 2 hours

Filter dried catalyst was dried in the oven at 90° C. overnight

Dried catalyst was ground and sieved

Calcining Procedure

Catalyst was loaded in four 25 g portions into quartz tube reactor (QRU). The QRU was purged under bulk nitrogen for several hours and then switched to purified nitrogen (bulk nitrogen passed through catalyst beds) for two days to ensure a sufficiently oxygen free environment for calcination. The purified nitrogen flow was 400 sccm. The heating program used was: RT to 600° C. in 6 hours and held at 600° C. for 2 hours, then cooled to room temperature by convective cooling.

Four boats loaded with catalyst were loaded into quartz tube according to the scheme as shown in FIG. 1.

The heating zone where the 4th boat was located was not heated. The estimated temperature for calcination in boat 4 was from 400 to 525° C. The first two boats were calcined via the usual calcination procedure at 600° C. Boat #3 and #4 were covered with ceramic membrane material (glass wool), which resulted in lower flow of nitrogen above (over) the catalyst precursor. Additionally, activated carbon was placed on the top of the ceramic membrane material over boat 4 to scavenge any oxygen released from the surface of non-calcined catalyst.

FIG. 2 is an X ray diffraction pattern (XRD) for the uncalcined catalyst sample. The figure also contains a baseline of an XRD of a typical calcined catalyst. In FIG. 2 the relatively sharper peak to the left side of the XRD is the M1 phase. The larger broader peek to the right is the M2 phase. The sample of low or partially calcined catalyst from boat 4 has a broader M2 peek than that of a calcined catalyst.

The catalyst produced from boat 4 was tested in a lab scale dehydrogenation reactor (Micro reactor unit—MRU) and the results are compared to a conventional calcination process. The results are set forth in Table 1.

TABLE 1 Activity and Selectivity Comparison Between Baseline Example and Inventive Example at 25% Conversion Inventive Example Baseline Example Temperature at 25% conversion 330° C. 380° C. Selectivity at 25% conversion ^(†) 87% 98%

The catalyst calcined in accordance with the procedures of the current application were tested in a long term oxidative dehydrogenation reactor together with two baseline samples (a conventionally calcined catalyst and an un-calcined catalyst). The results are set forth in table 2 below.

TABLE 2 Summary of Performance Comparisons Between Inventive Example and Conventionally Calcined Catalyst and Un-Calcined Catalyst Conditions Inventive Example Conventionally Calcined Catalyst Un-calcined catalyst Conversion and 25% conversion is at 24% conversion is at 367° C. and After 8 h, temperature at 21.6 selectivity of fresh catalyst 330° C. and 3000 h⁻¹ space 3000 h⁻¹ with 97% selectivity wt. % conversion increased (Reference Point) velocity with selectivity 87% from 340 C. to 370 C., with selectivity toward ethylene decreased from 82.7 wt % to 77.35 wt % Stability No changes to conversion Conversion decreased by 5% Did not last longer than 8 h (before changing of and selectivity at 25% and selectivity dropped by 2.43% after conditions) ethane conversion after 193 h run length 150 hours on stream at conditions above Oxygen depletion No changes to conversion Both conversion and selectivity NA condition and selectivity after 60 decreased by 3.5% at 367° C. after 259 (Testing catalyst to hours on stream after hours on oxygen depleting condition low O₂ content in the back to original conditions product, i.e. less than 100 ppm) Air regen Air regens fully recover Air regen did not result in a full (Regen done after the catalyst performance, recovery of the original catalyst conditions are even after oxygen performance but rather results in changed, i.e. exposed depleting environment noticeable decrease of selectivity to oxygen depleted operation toward ethylene over time conditions.

The un-calcined catalyst had good conversion—25% conversion at 340° C. which is very completive with the conversion for the sample in accordance with the present disclosure (low calcined catalyst). However, the catalyst died after about 8 hours testing.

The testing shows the catalyst calcined in accordance with the present application has a better stability than the baseline catalyst and is fully regeneratable with oxygen.

A sample of catalyst obtained from boat 4 was in a micro reactor unit (MRC) ethane oxidative dehydrogenation unit in a longer term run with several in situ air regenerations of the catalyst. The results are shown in FIG. 3. In FIG. 3, the upper line is the selectivity to ethylene at 25% conversion and the lower line is conversion at the temperature specified in the sections of the graph. At 300° C. the conversion is slightly below 25%. At 320° C. the conversion is slightly below 25%. The temperature of the reactor was increase to 375° C. so that there was no residual oxygen the product stream leaving the reactor. At 375° C. the conversions is around 28%. For part of the experiment dimethyl disulphide (DMDS) was injected with the feed. And the temperature was reduced to 356° C. and the conversion dropped slightly. Throughout the run the selectivity was in the 88 to 90% range.

The number following the temperature is hourly space velocity of the feed gas (ethylene and oxygen). The vertical darker bars show air regeneration.

The catalyst showed excellent stability/robustness even on regeneration and in the presence of DMDS.

The pore size of the base line catalyst and the catalyst of the present disclosure before and after testing in an ethylene dehydrogenation unit were measured using BET. The results are shown in FIG. 4. The results show the catalyst according to the present disclosure has majority of small pores less than 10 nm. After testing the volume of pores less than 10 nm has decreased but is still larger than the base line catalyst. In use the pore size of the base line catalyst is further reduced.

The following table show the reaction conditions and results for the trial.

TABLE 3 Long Term Oxidative Dehydrogenation of Ethane on Microreactor Unit (MRU) Using Inventive Catalyst Reactor Unit 25% Reactor conditions and space Temperature Conversion Selectivity Conversion Selectivity rational behind the velocity Range ( ° C.) Range (%) Range (%) Temperature at 25% condition changes Day(s) ( h⁻¹) min max min max min max (° C.) Conversion Screening and establishing Day 3000 280 330 8.04 24.15 88.26 92.80 332 87.5 standard run conditions 1 (25% Conversion Temperature at 3000 h-1 space velocity) Held run at stable Days 3000 330 23.30 24.15 88.26 89.09 conditions of 330 C. for 5 2-6 days Activity decreased from 24.15 to 23.30% conversion Air regen: 380 C. at Day 380 250 sccm for 5 h then 6 decrease to 320 C. and leave it under air overnight. Re-establishing standard Day 3000 280 355 6.59 25.00 89.43 96.97 355 89.43 run conditions 7 (25% Conversion Temperature at 3000 h⁻¹ space velocity) Started to decrease feed Day 1500 280 320 8.64 22.75 91.96 95.91 gas flow to target no 8 1070 320 25.02 91.64 residual oxygen left on Day 1070 320 25.02 26.58 91.16 91.64 outlet of reactor  9-10 Left under stable no Day 1500 320 21.57 22.18 91.48 92.21 residual oxygen conditions 10-15 for 5 days Re-establishing standard Day 3000 320 355 12.83 25.01 89.74 93.7 355 89.74 run conditions 15 (25% Conversion Temperature at 3000 h⁻¹ space velocity) Allowed reactor to run Day 3000 355 24.43 89.91 under standard conditions 16 over night Started to increase Day 3000 355 375 24.43 26.8 86.51 89.91 temperature to target no 16 residual oxygen left on outlet of reactor Left under stable no Days 3000 375 26.72 27.05 88.04 88.4 residual oxygen conditions 16-23 for 7 days Re-establishing standard Day 3000 355 375 21.46 26.76 88.33 89.51 365 88.9 run conditions 23 (25% Conversion Temperature at 3000 h⁻¹ space velocity) Air regen: 380 C. at Day 380 250 sccm for 5 h then 23 decrease to 320 C. and leave it at this temperature under air overnight. Re-establishing standard Day 3000 300 368 8.57 25.48 88.65 96.77 364 88.8 run conditions (25% 24 Conversion Temperature at 3000 h⁻¹ space velocity) Held under air at 300 C. Day 300 over weekend to avoid 24-26 consuming ethane Re-establishing standard Day 3000 330 365 15.06 25.17 88.88 92.27 364 88.9 run conditions 26 (25% Conversion Temperature at 3000 h⁻¹ space velocity) Allowed reactor to run Day 3000 365 25.95 89.06 under standard conditions 26-30 for 3 days before DMDS injection Conditions during DMDS Day 3000 365 24.42 24.76 89.06 89.31 injection 30 Conditions after DMDS Day 3000 365 24-29 24.36 89.28 89.4 injection 30

Testing was carried out over 30 days under various conditions (no residual oxygen or exposure to sulfur-containing environments) to demonstrate robustness of catalyst. Standard conversion conditions were established at start of run to create a reference point, i.e. at 3000 h⁻¹ flow, what temperature is needed to achieve 25% conversion. After catalyst was exposed to unfavorable conditions, the reference conditions were revisited to see what temperature was needed to achieve 25% conversion. Re-establishing the reference conditions provided a means of evaluating how the catalyst was responding to testing. An increase in 25% conversion temperature is acceptable as long as the temperature stays the same/below the threshold value (conversion temperature of standard catalyst) and has selectivity that is better than a standard catalyst run over similar long-term and oxygen-deprived conditions. 

What is claimed is:
 1. A method to calcine a catalyst precursor of the formula Mo₁V_(0.1-1)V_(0.1-1)Nb_(0.1-1)Nb_(0.1-1)Te_(0.01-0.2)X_(0.2)O_(d) where X is chosen from Pd, Sb Ba, Al, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, Ca, oxides thereof and mixtures thereof, and d is a number to satisfy the valence of the catalyst while maintaining an amorphous content of not less than 40 wt. % the method comprising calcining the catalyst precursor in an inert container with flow passage there through, at a rate from 0.5 to 10° C. per minute from room temperature to a holding temperature from 370° C. to 540° C. under a stream of pre heated gas chosen from steam and inert gas and mixtures thereof at a rate of flow comparable to a flow rate of not less 150 sccm through a 2.54 cm diameter tube, with a length of 152 cm at a pressure of greater than or equal to 1 psig having a temperature from 300° C. to 540° C.; holding the catalyst precursor at the holding temperature for at least 2 hours; and cooling the catalyst precursor to room temperature said catalyst precursor being fully or partially enclosed by a porous material having a melting temperature greater than 600° C.
 2. The method according to claim 1, wherein the inert container is made from high temperature glass, quartz, ceramics, or steel.
 3. The method according to claim 2, wherein the inert container has a heat conductivity greater than 0.34 W m⁻¹·K.
 4. The method according to claim 1, wherein the pressure of inert gas is greater than 1 psig.
 5. The method according to claim 4, wherein rate for heating the catalyst precursor is 0.9 to 2.0 C per min.
 6. The method according to claim 4, wherein the catalyst precursor is held at the holding temperature from 2-24 hours.
 7. The method according to claim 6, wherein the holding temperature is from 400° C. to 525° C.
 8. The method according to claim 7, wherein the inert gas and comprises nitrogen.
 9. The method according to claim 8, wherein the porous material is chosen from glass and mineral fiber.
 10. The method according to claim 9, wherein charcoal or activated carbon is on the outer surface of the porous material in an amount up to 0.5 g per 1 g of catalyst precursor is present on the upper surface of the material.
 11. The method according to claim 10, wherein X is one or more metals and oxides thereof are chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof.
 12. The method according to claim 11, wherein the molar ratio of said one or more metals and oxides chosen from Pd, Sb, Ba, Al, Cu, Ti, Fe, Ca, Zr and mixtures thereof to Mo is from 1:0.001-0.3.
 13. The method according to claim 12, wherein the X is chosen from of one or more metals and oxides thereof are chosen from Pd, Sb, Ba, Al, Cu and mixtures thereof.
 14. The method according to claim 13, wherein in the catalyst precursor X is absent.
 15. The method according to claim 14, wherein the catalyst precursor has the formula: MoV_(1.0)V_(0.10-049)Te_(0.06-0.17)Nb_(0.13-0.19)O_(d).
 16. A calcined catalyst of the formula: Mo₁V_(0.40-0.45)Te_(0.10-0.16)Nb_(0.13-0.16)O_(d).
 17. A calcined catalyst of the formula MoVo_(0.40-0.45)Te_(0.10-0.16)Nb_(0.13-0.16)O_(d) having an amorphous content of not less than 40 wt. %.
 18. A calcined catalyst according to claim 17 having a crystallite size calculated according to the Scherrer equation of 45 to 55 nm.
 19. A calcined catalyst according to claim 17 having a crystallite size calculated according to the Scherrer equation of 50 to 52 nm.
 20. The calcined catalyst of claim 18 wherein the catalyst is bound, agglomerated, filled, promoted, impregnated, supported with from 5 to 90 wt. % of a material other than active phase.
 21. A method for the oxidative dehydrogenation of a mixed feed comprising one or more C₂₋₄ paraffins and oxygen in a volume ratio from 70:30 to 95:5 and optionally one or more C₃₋₆ alkanes or alkenes and oxygenated species including CO and CO₂ at a temperature from 320° C. up to 385° C., a gas hourly space velocity of not less than 100 hr⁻¹, and a pressure from 0.8 to 7 atmospheres comprising passing said mixture over the catalyst of claim
 1. 22. A method for the oxidative dehydrogenation of a mixed feed comprising one or more C₂₋₄ paraffins and oxygen in a volume ratio from 70:30 to 95:5 and optionally one or more C₃₋₆ alkanes or alkenes and oxygenated species including CO and CO₂ at a temperature from 320° C. up to 385° C., a gas hourly space velocity of not less than 100 hr⁻¹, and a pressure from 0.8 to 7 atmospheres comprising passing said mixture over the catalyst of claim
 17. 